Color photographic recording material

ABSTRACT

A color photographic material which contains on a support at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, together with customary non-light-sensitive layers, characterized in that at least one layer contains a compound of formula (I) or (II) wherein the R 1 -radicals and R 2 -radicals are preferably methyl; and wherein the compounds of formula (II) are preferably (III) R 3  is a radical —CH(CH 3 )—X—D, wherein X is phenylene. D is a group (IV) or a group —C(O)—C 1 –C 18 alkyl or a group —O—CH 2 —CH(OH)—CH 2 —NR 12 R 13 , with R 12  and R 13  being C 1 –C 18 alkyl or together form a 4 to 8 membered ring as defined in claim 1, or D is a group —O—CH 2 —CH(OH)—CH 2 —N(R 12 )—CH 2 —CHOH—CH 2 —O—or —O—CH 2 —CH(OH)—CH 2 —W—CH 2 —CHOH—CH 2 —O— with W being a divalent amino group (—N(C 1 –C 18 alkyl)−), a polyamine residue, a polyethyleneimine residue or a polyoxyalkyleneamine residue; Z and Z′ are for example C 1 –C 12 alkyl, C 3 –C 12 alkenyl, C 3 –C 12 alkenyl, C 5 –C 8 cycloalkyl, or Z and Z′ together bivalent groups such as —CH 2 —CH 2 — or —CH 2 —C(R 18 )(R 19 )—CH(R 20 )—

The present invention relates to a colour photographic recordingmaterial with improved colour stability.

Colour photographic materials customarily contain at least one yellowcoupler, at least one magenta coupler and at least one cyan coupler,from which the corresponding dyes are produced by exposure anddevelopment. These dyes should exhibit high stability upon prolongeddark storage or light exposure, in order to avoid prematuredeterioration of the photographic image. In particular, yellow dyesproduced from couplers with an open-chain ketomethylene grouping must bestabilized both against light and dark fading. Various substances havealready been proposed to achieve this object, e.g. bisphenol derivativesas disclosed in U.S. Pat. Nos. 3,700,455 and 4,782,011, epoxy compoundsas taught in U.S. Pat. Nos. 5,316,903 and 5,183,731, phenolic thianederivatives as reported in U.S. Pat. No. 5,070,007, and hindered aminecompounds as disclosed in DE 2654058, U.S. Pat. No. 4,268,593 and RD319902. However, the effect achieved with them is still inadequate andthere is continued interest for more effective stabilizers.

It has now been found that certain glycidyl or alkylcarbonyl functionalnitroxyl derivatives are able to provide yellow photographic dyes withoutstanding resistance against light and dark fading.

The present invention thus pertains to a colour photographic materialwhich contains on a support at least one blue-sensitive silver halideemulsion layer containing at least one yellow coupler, at least onegreen-sensitive silver halide emulsion layer containing at least onemagenta coupler, at least one red-sensitive silver halide emulsion layercontaining at least one cyan coupler, together with customarynon-light-sensitive layers, characterized in that at least one layercontains a compound of the formula (I) or (II)

wherein

-   the R₁-radicals are each independently of one another hydrogen,    halogen, NO₂, cyano, —CONR₅R₆, —(R₉)COOR₄, —C(O)—R₇, —OR₈, —SR₈,    —NHR₈, —N(R₈)₂, carbamoyl, di(C₁–C₁₈alkyl)carbamoyl, —C(═NR₅)(NHR₆);    -   unsubstituted C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈alkynyl,        C₇–C₉phenylalkyl, C₃–C₁₂cycloalkyl or C₂–C₁₂heterocycloalkyl; or    -   C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈ alkynyl, C₇–C₉phenylalkyl,        C₃–C₁₂ cycloalkyl or C₂–C₁₂heterocycloalkyl, which are        substituted by NO₂, halogen, amino, hydroxy, cyano, carboxy,        C₁–C₄alkoxy, C₁–C₄alkylthio, C₁–C₄alkylamino or        di(C₁–C₄alkyl)-amino; or    -   phenyl, naphthyl, which are unsubstituted or substituted by        C₁–C₄alkyl, C₁–C₄alkoxy, C₁–C₄alkylthio, halogen, cyano,        hydroxy, carboxy, C₁–C₄alkylamino or di(C₁–C₄alkyl)amino;    -   R₄ is hydrogen, C₁–C₁₈alkyl, phenyl, an alkali metal cation or a        tetraalkyl-ammonium cation;    -   R₅ and R₆ are hydrogen, C₁–C₁₈alkyl, C₂–C₁₈alkyl, which is        substituted by at least one hydroxy group or, taken together,        form a C₂–C₁₂alkylene bridge or a C₂–C₁₂-alkylene bridge        interrupted by at least one O or/and NR₈ atom;    -   R₇ is hydrogen, C₁–C₁₈alkyl or phenyl;    -   R₈ is hydrogen, C₁–C₁₈alkyl or C₂–C₁₈alkyl which is substituted        by at least one hydroxy group;    -   R₉ is C₁–C₁₂alkylene or a direct bond; or-   all the R₁-radicals form together the residue of a polycyclic    cycloaliphatic ring system or a polycyclic heterocycloaliphatic ring    system with at least one di- or trivalent nitrogen atom;-   the R₂-radicals are independently of each other C₁–C₆alkyl or    phenyl;-   R₃ is a radical of the formula —C(R₁₀)(R₁₀)—X—D, wherein    -   X is phenylene, naphthylene or biphenylene, which are        unsubstituted or substituted by NO₂, halogen, amino, hydroxy,        cyano, carboxy, C₁–C₄alkoxy, C₁–C₄alkylthio, C₁–C₄alkylamino or        di(C₁–C₄alkyl)amino;    -   the R₁₀-radicals are independently of each other H or CH₃;    -   D is a group

-   -   -   a group C(O)—C₁–C₁₈alkyl,        -   a group C(O)—R₁₁—C(O)—C₁–C₁₈alkyl; with R₁₁, being a bond or        -   C₁–C₁₂alkylene, or        -   a group —O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, wherein        -   R₁₂ and R₁₃ independently of one another are unsubstituted            C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈alkynyl, phenyl,            C₇–C₉phenylalkyl, C₃–C₁₂cycloalkyl; the radicals may be            interrupted once or more than once by —, —NH—, —O—, —S—,            —CO—, —SO—, —SO₂—, or            -   C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈ alkynyl, phenyl,                C₇–C₉phenylalkyl, C₃–C₁₂cycloalkyl, which are                substituted by halogen, amino, hydroxy, carboxy,                C₁–C₆alkoxy, C₁–C₆alkoxycarbonyl, C₁–C₆alkylthio,                C₁–C₆alkylamino or di(C₁–C₆alkyl)-amino,                C₁–C₆alkylamino-carbonyl or                di(C₁–C₆alkyl)-amino-carbonyl; the radicals may be                interrupted once or more than once by —, —NH—, —O—, —S—,                —CO—, —SO—, —SO₂—, or            -   R₁₂ and R₁₃ together with N form a 4 to 8 membered ring,                whereby the ring may be interrupted by —O—, —NH—, S—,                —CO—, —SO—, —SO₂ and may be sustituted by carboxy, or

    -   D is a group —O—CH₂—CH(OH)—CH₂—N(R₁₂)—CH₂—CHOH—CH₂—O— or        O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O— with W being a divalent amino        group (—N(R₁₂)-), a polyamine residue, a polyethyleneimine        residue or a polyoxyalkyleneamine residue;

-   A is a divalent group required to form a cyclic 5-, 6- or 7-membered    ring, whereby the divalent group is selected from C₂–C₄alkylene,    C₂–C₄alkenylene, C₂–C₄alkinylene, 1,2 phenylene which may be    unsubstituted or substituted by NO₂, halogen, amino, hydroxy, cyano,    carboxy, carbonyl, C₁–C₁₈alkoxy, C₁–C₁₈ acyloxy, benzoyloxy,    C₁–C₁₈alkylthio, C₁–C₁₈alkylamino or di(C₁–C₁₈alkyl)amino, or    phenyl; or    -   A is a group —CH₂—CHY—CH₂—, wherein    -   Y is H, OH, OR₁₄, NR₁₅R₁₆, —O—C(O)—R₁₇ or NR₁₅—C(O)—R₁₇;        -   R₁₄ is C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈alkenyl, phenyl,            benzyl, mesityl, or C₂–C₁₈alkyl which is substituted by at            least one hydroxy group;        -   R₁₅ and R₁₆ independently are hydrogen, C₁–C₁₈alkyl,            C₂–C₁₈alkenyl, C₂–C₁₈alkenyl, or taken together form a            C₂–C₁₂alkylene bridge or a C₂–C₁₂alkylene bridge interrupted            by at least one O atom;        -   R₁₇ is phenyl, benzyl, mesityl, C₁–C₁₈alkyl, C₂–C₁₈alkenyl,            C₂–C₁₈alkinyl; or    -   A is a group —CH₂—C(OZ)(OZ′)—CH₂—, wherein Z and Z′ are        independently C₁–C₁₂alkyl, C₃–C₁₂alkenyl, C₃–C₁₂alkinyl,        C₅–C₈cycloalkyl, phenyl, naphthyl, C₇–C₉phenylalkyl; or Z and Z′        together form one of the bivalent groups —C(R₁₈)(R₁₉)—CH(R₂₀)—,        CH(R₁₈)—CH₂—C(R₁₉)(R₂₀)—, —CH(R₁₉)—CH₂—C(R₁₈)(R₂₀)—,        —CH₂—C(R₁₈)(R₁₉)—CH(R₂₀)—, o-phenylene, 1,2-cyclohexylidene,        —CH₂—CH═CH—CH₂—        -   or

wherein

-   -   -   R₁₈ is hydrogen, C₁–C₁₈alkyl, COOH, COO—(C₁–C₁₈)alkyl,            OCO—(C₁–C₁₈)alkyl or CH₂OR₂₁;        -   R₁₉ and R₂₀ are independently hydrogen, C₁–C₁₂alkyl, COOH or            COO—(C₁–C₁₂)-alkyl;        -   R₂₁ is hydrogen, C₁–C₁₈alkyl, C₅–C₆cycloalkyl, benzyl, or a            monovalent acyl residue derived from an aliphatic,            cycloaliphatic or aromatic monocarboxylic acid having up to            18 carbon atoms; or        -   Z and Z′ together form one of the tetravalent groups

wherein

-   Q is a bisacyl residue which is derived from a C₂–C₁₂dicarboxylic    acid or C₁–C₁₂alkylene.

DEFINITIONS

Halogen is fluoro, chloro, bromo or iodo.

The alkyl radicals in the various substituents may be linear orbranched. Examples of alkyl containing 1 to 18 carbon atoms are methyl,ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl,2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

The alkenyl radicals in the various substituents may be linear orbranched. Examples of C₂–C₁₈alkenyl are vinyl, allyl, 2-methylallyl,butenyl, hexenyl, undecenyl and octadecenyl. Preferred alkenyls arethose, wherein the carbon atom in the 1-position is saturated and wherethe double bond is not activated by substituents like O, C═O, and thelike.

Examples of C₂–C₁₈alkynyl are ethynyl, 2-butynyl, 3-hexynyl,5-undecynyl, 6-octadecynyl. The alkynyl radicals may be linear orbranched.

C₇–C₉phenylalkyl is for example benzyl, phenylpropyl, a,a-dimethylbenzylor a-methylbenzyl.

C₃–C₁₂cycloalkyl which is unsubstituted or substituted by 1, 2 or 3C₁–C₄alkyl is e.g. cyclopropyl, cyclopentyl, methylcyclopentyl,dimethylcyclopentyl, cyclohexyl, methylcyclohexyl.

Alkyl substituted by —OH is typically 2-hydroxyethyl, 2-hydroxypropyl or2-hydroxybutyl. C₁–C₁₈Alkyl substituted by C₁–C₈alkoxy, preferably byC₁–C₄alkoxy, in particular by methoxy or ethoxy, is typically2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.

C₁–C₁₈Alkyl substituted by di(C₁–C₄alkyl)amino is preferably e.g.dimethylamino, diethylamino, 2-dimethylaminoethyl, 2-diethylaminoethyl,3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and4-diethylaminobutyl.

C₁–C₁₈Alkyl substituted by C₁–C₄alkylamino is preferably e.g.methylamino, ethylamino, 2-methylaminoethyl, 2-ethylaminoethyl,3-methylaminopropyl, 3-ethylaminopropyl, 3-butylaminopropyl and4-ethylaminobutyl.

C₁–C₈Alkoxy and, preferably C₁–C₄alkoxy, are typically methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,heptoxy or octoxy. C₁–C₄Alkylthio is typically thiomethyl, thioethyl,thiopropyl, thioisopropyl, thiobutyl and thioisobutyl.

C₂–C₁₂Heterocycloalkyl is typically oxirane, 1,4-dioxane,tetrahydrofuran, γ-butyrolactone, ε-caprolactam, oxirane, aziridine,diaziridine, pyrrole, pyrrolidine, thiophen, furan, pyrazole, imidazole,oxazole, oxazolidine, thiazole, pyran, thiopyran, piperidine ormorpholine.

Examples of C₂–C₁₂alkylene bridges, preferably of C₂–C₆alkylene bridges,are ethylene, propylene, butylene, pentylene, hexylene.

C₂–C₁₂alkylene bridges interrupted by at least one N or O atom are, forexample, —CH₂—O—CH₂—CH₂, —CH₂—O—CH₂—CH₂—CH₂, —CH₂—O—CH₂CH₂—CH₂—CH₂—,—CH₂—O—CH₂—CH₂—O—CH2—, —CH₂—NH—CH₂—CH₂, —CH₂—NH—CH₂—CH₂—CH₂—,—CH₂—NH—CH₂—CH₂—CH₂—CH₂—, —CH₂—NH—CH₂—CH₂—NH—CH2— or—CH₂—NH—CH₂—CH₂—O—CH₂—. Alkenyl having from 3 to 12 carbon atoms is abranched or unbranched radical, for example propenyl, 2-butenyl,3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl,n-2-octenyl, n-2-dodecenyl, isododecenyl.

Alkinyl having from 3 to 12 carbon atoms is a branched or unbranchedradical, for example propinyl (—CH₂—C≡CH), 2-butinyl, 3-butinyl,n-2-octinyl or n-2-dodecinyl.

C₇–C₉phenylalkyl is for example benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl, benzyl is preferred.

C₁–C₁₂alkylene is a branched or unbranched radical, for examplemethylene, ethylene, propylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,decamethylene or dodecamethylene.

C₅–C₈cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl,methylcyclopentyl or cyclooctyl.

Examples of a monocarboxylic acid having up to 18 carbon atoms areformic acid, acetic acid, propionic acid, the isomers of valeric acid,methyl ethyl acetic acid, trimethyl acetic acid, capronic acid, lauricacid or stearic acid. Examples for unsaturated aliphatic acids areacrylic acid, methacrylic acid, crotonic acid, linolic acid and oleicacid.

Typical examples of cycloaliphatic carboxylic acids are cyclohexanecarboxylic acid or cyclopentane carboxylic acid.

Examples of aromatic carboxylic acids are benzoic acid, salicylic acidor cinnamic acid.

Examples of dicarboxylic acids are oxalic acid, malonic acid, succinicacidglutaric acid adipic acid, sebatic acid, fumaric acid, maleic acid,phthalic acid, isophthalic acid, terephthalic acid.

Examples for C₄–C₁₂cycloalkanone-yl are cyclopentanone-yl,cyclohexanone-yl or cycloheptanone-yl.

Phenyl substituted by 1, 2 or 3 C₁–C₄alkyl or C₁–C₄alkoxy is typicallymethylphenyl, dimethylphenyl, trimethylphenyl, t-butylphenyl,di-t-butylphenyl, 3,5-di-t-butyl-4-methylphenyl, methoxyphenyl,ethoxyphenyl and butoxyphenyl.

Examples of polycyclic cycloaliphatic ring systems are adamantane,cubane, twistane, norbornane, bicyclo[2.2.2]octane orbicyclo[3.2.1]octane.

An example of a polycyclic heterocycloaliphatic ring system ishexamethylentetramine (urotropine).

Examples of a bisacyl residue which is derived from a C₂–C₁₂dicarboxylicacid are: —(O)C—(CH₂)₁₋₆—C(O)—, —(O)C-phenylene-C(O)—.

Concerning the group W, examples for polyamines are ethylenediamine,N-methylethylenediamine, N,N′-dimethylethylenediamine,N-methyl-1,3-propanediamine, N,N′-dimethyl-1,3-propanediamine,N,N′-dimethyl-1,6-hexanediamine, diethylenetriamine,3,3′-imino-bis-propylamine, spermidine, bis(hexamethylene)triamine,triethylenetetramine, N,N′-Bis(3-aminopropyl)-ethylenediamine, spermine,tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine,4,4′-methylenebis(cyclohexylamine), 1,4-diaminocyclohexane,N-cyclo-hexyl-1,3-propanediamine, 1,8-diamino-p-menthane,N,N′-diethyl-2-butene-1,4-diamine, 2,2′-oxy-bis(ethylamine),4,7,10-trioxa-1,13-tridecanediamine,N,N′-bis(2-hydroxyethyl)ethylenediamine, 4,4′-bipiperidine, piperazine,1,4,7-triazacyclononane, 1,3-diaminoaceton, 1,4-phenylendiamine,N,N′-dibenzylethylenediamine or m-xylylenediamine.

Polyoxyalkyleneamines are amine terminated polyethers and refer tomonoamine, diamine, or triamines. They are commercially available underthe tradename JEFFAMINE™ from Huntsman Corp. Zaventem, Belgium.

Examples for the group D being —O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, wherein R₁₂and R₁₃ together with N form a 4 to 8 membered ring, are:

When the divalent group A has the meaning of C₂–C₄alkylene orC₂–C₄alkenylene, these groups may also be interrupted by an O or N atom.

C₂–C₄alkylene bridges interrupted by at least one N, O atom are, forexample, —CH₂—O—CH₂—CH₂, —CH₂—O—CH₂—, —O—CH₂—CH₂—, —O—CH₂—O—CH2—,—CH₂—NH—CH₂—, —CH₂NH—CH₂—CH₂—, —NH—CH₂—CH₂—, —NH—CH₂—NH—CH2— or—CH₂—NH—CH₂—.

Preferred Compounds I

Preferred are compounds of the formula (I), wherein the group

is

Most preferred are compounds of the formula I, wherein all R₁ radicalsare methyl and

-   R₃ is a radical —CH(CH₃)—X—D wherein X is phenylene,    -   D is a group

or a group —C(O)—C₁–C₁₈alkyl or a group —O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, withR₁₂ and R₁₃ being C₁–C₁₈alkyl or together form a 4 to 8 membered ring asdefined above, or

-   -   D is a group —O—CH₂—CH(OH)—CH₂—N(R₁₂)—CH₂—CHOH—CH₂—O— or        —O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O— with W being a divalent        amino group (—N(C₁–C₁₈alkyl)-), a polyamine residue, a        polyethyleneimine residue or a polyoxyalkyleneamine residue.

An example of a suitable compound of formula (I) is

Compounds IIa

Compound IIa is a compound II wherein R₂ is methyl and A is a group—CH₂—CHY—CH₂—

-   Y and R₃ are as defined above.    Preferred Compounds IIa

Preferred are compounds of the formula IIa, wherein

-   Y is H, OH, OR₁₄, —O—C(O)—R₁₇;-   R₁₄ is C₁–C₁₈alkyl, phenyl, benzyl, mesityl,-   R₁₇ is C₁–C₁₈alkyl, phenyl, benzyl, mesityl,-   R₃ is a radical —CH(CH₃)—X—D wherein X is phenylene,    -   D is a group

-   -    or a group —C(O)—C₁–C₁₈alkyl or a group        —O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, with R₁₂ and R₁₃ being C₁–C₁₈alkyl or        together form a 4 to 8 membered ring as defined above, or    -   D is a group —O—CH₂—CH(OH)—CH₂—N(R₁₂)—CH₂—CHOH—CH₂—O— or        —O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O— with W being a divalent        amino group (—N(C₁–C₁₈alkyl)-), a polyamine residue, a        polyethyleneimine residue or a polyoxyalkyleneamine residue.

Examples of compounds of the formula IIa

Compounds IIb.

Compound IIb is a compound II, wherein R₂ is methyl and A is a group

-   Z, Z′ and R₃ are as defined above.

Preferred are compounds of the formula IIb are those wherein

-   R₃ is a radical —CH(CH₃)—X—D wherein X is phenylene,    -   D is a group

-   -    or a group —C(O)—C₁–C₁₈alkyl or a group        —O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, with R₁₂ and R₁₃ being C₁–C₁₈alkyl or        together form a 4 to 8 membered ring as defined above, or    -   D is a group —O—CH₂—CH(OH)—CH₂—N(R₁₂)—CH₂—CHOH—CH₂—O— or        O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O— with W being a divalent amino        group (—N(C₁–C1₈alkyl)-), a polyamine residue, a        polyethyleneimine residue or a polyoxyalkyleneamine residue.

Examples of compounds IIb, wherein Z and Z′ are the same radicals andare C₁–C₁₂alkyl, C₃–C₁₂alkenyl, C₅–C₈cycloalkyl, benzyl; and R₃ is—CH(CH₃)—X—D, X is phenylene, are:

-   1.)    4,4-Dimethoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   2.)    4,4-Diethoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   3.)    2,2,6,6-Tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-4,4-dipropoxy-piperidine

-   4.)    4,4-Dibutoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   5.)    4,4-Diisobutoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   6.)    2,2,6,6-Tetramethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   7.)    4,4-Bis-allyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   8.)    4,4-Bis-cyclohexyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   9.)    4,4-Bis-benzyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

Examples of compounds IIb, wherein Z and Z′ together form one of thebivalent groups —C(R₁₈)(R₁₉)—CH(R₂O)— or o-phenylene or1,2-cyclohexylidene and R₃ is —CH(CH₃)—X—D, X is phenylene, are:

-   1.)    7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   2.)    2,7,7,9,9-Pentamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   3.)    2-Ethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   4.)    7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-2-propyl-1,4-dioxa-8-aza-spiro[4.5]decane

-   5.)    2-Butyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   6.)    7,7,9,9-Tetramethyl-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   7.)    2-Decyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   8.)    2-Dodecyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   9.)    (7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-yl)-methanol

-   10.)    2-Methoxymethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   11.)    2–Cyclohexyloxymethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   12.)    2-Benzyloxymethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   13.) Acetic acid    7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro4.5]dec-2-ylmethyl    ester

-   14.) Octadecanoic acid    7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl    ester

-   15.) Benzoic acid    7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl    ester

-   16.)    2,2,7,7,9,9-Hexamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   17.)    2,3,7,7,9,9-Hexamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

-   18.)    4,4-(o-Phenylendioxy)-2,2,6,6-tetramethyl-1-[1′-(4′-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   19.)    4,4-(1′,2′-cyclohexylendioxy)-2,2,6,6-tetramethyl-1-[1″-(4″-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

-   20.)    7,7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane-2,3-dicarboxylic    acid dimethyl ester

Examples of compounds IIb, wherein Z and Z′ together form one of thebivalent groups —CH₂—C(R₁₈)(R₁₉)—CH(R₂₀)—, o-phenylene or1,2-cyclohexylidene, —CH₂—CH═CH—CH₂— or

and R₃ is —CH(CH₃)—X—D, X is phenylene, are:

-   1.)    8,8,10,10-Tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

-   2.)    3,3,8,8,10,10-Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

-   3.)    1-Dimethylamino-3-{4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5undec-9-yloxy)-ethyl]-phenoxy}-propan-2-ol1-Dimethylamino-3-{4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenoxy}-propan-2-ol

-   4.)    1-{4-[1-(3,3,8,8,10,10-Hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenoxy}-3-pyrrolidin-1-yl-propan-2-ol

-   5.)    1-Diethylamino-3-{4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenoxy}-propan-2-ol

-   6.)    3-Ethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

-   7.)    3,3-Diethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

-   8.)    3,8,8,10,10-Pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-3-propyl-1,5-dioxa-9-aza-spiro[5.5]undecane

-   9.)    3-Butyl-3-ethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa    -9-aza-spiro[5.5]undecane

-   10.)    2,2,4,4-Tetramethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza-dispiro[5.2.5.2]hexadec-11-ene

-   11.)    {3,8,8,10,10-Pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

-   12.)    {3-Ethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-yl}-methanol

-   13.)    3-Methoxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

-   14.)    3-Cyclohexyloxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

-   15.)    3-Benzyloxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

-   16.) Acetic acid    3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl    ester

-   17.)    3,8,8,10,10-Pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane-3-carboxylic    acid methyl ester

-   18.)    8,8,10,10-Tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane-3,3-dicarboxylic    acid diethyl ester

-   19.)    2,2,4,4-Tetramethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3-aza-spiro[5.6]dodec-9-ene

Examples of compounds IIb, wherein Z and Z′ together form a tetravalentgroup are:

-   1.) Octanedioic acid    bis-{7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}ester

2.) Terephthalic acidbis-{7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl}ester

-   3.)    1′,4′-Bis-{7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl)-oxybutane

-   4.) Octanedioic acid    bis-{3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}ester

-   5.)    1′,6′-Bis-{8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane

-   6.)    3,3-Bis-{8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza}-spiro[5.5]undecane

Further Examples of compounds II are:

New Compounds

Compounds of the formula II, wherein D is a group—O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃ or a group —O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O—with W being a divalent amino group (—N(R₁₂)—, a polyamine residue, apolyethyleneimine residue or a polyoxyalkyleneamine residue.

Preparation:

Compounds according to formula (I) or (II) may be prepared in differentways according to known methods. These methods are for example describedin Macromol. Rapid Commun. 17, 149, 1996, Macromol Symp. 111, 47,(1996), Polym. Degr. Stab. 55, 323 (1997), Synlett 1996, 330, U.S. Pat.No. 5,498,679 or U.S. Pat. No. 4,921,962.

The starting compounds, which are phenylglycidylethers are known andeither commercially available or may be prepared according to EP 226543.

Synthesis of compounds II, especially of compounds IIa, wherein D is agroup

is described in WO 99/46261.

The preparation of the compounds of the formula IIb is carried outaccording to known reaction steps. A general method for the preparationis described in the Publication WO02/48109 (PCT ApplicationPCT/EP/01/13071).

The preparation starts from the 4-oxo compound XIIa which is a knowncompound described for example in DE 2352127.

The starting compound is reacted for example with suitable monoalcohols,diols or tetra-functional alcohols to form intermediates of formulaXIIb. Such ketalization reactions are well known in the art and thecorresponding compounds are mostly known. The reaction is for exampledescribed in U.S. Pat. Nos. 3,790,525, 3,899,464, 4,007,158 and4,105,626.

The compound of formula XIIb is oxidized according to standardprocedures to the corresponding nitroxide of formula XIIc, as forexample described in WO 99/46261.

The nitroxides are then reacted with a compound of formula

wherein R₁₀ is as defined above to obtain a compound of formula IIb.

This coupling reaction is also descriebed for example in GB 2335190 orin WO 99/46261.

The new compounds of formula II, wherein D is a group—O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃ or a group —O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O—with W being a divalent amino group (—N(R₁₂)—, a polyamine residue, apolyethyleneimine residue or a polyoxyalkyleneamine residue may beprepared by reaction of a compound of the formula II wherein D is agroup

with a monoamine, a polyamine residue, a polyethyleneimine residue or apolyoxyalkyleneamine residue in a suitable solvent.

The choice of the solvent is not critical. Examples are alcohols,ethers, THF and the like.

Examples of monoamines are NH₃ or primary amines like NH₂-alkyl,NH₂-alkenyl, NH₂-alkinyl, NH₂-aralkyl, NH₂-cycloalkyl, NH₂-Aryl, orsecundary amines like alkyl-NH-alkyl′ and mixed combinations with alkyl,alkenyl, alkinyl, cycloalkyl, aralkyl, aryl.

Alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl can be linear orbranched or unsaturated, or can be interrupted by N, O, S or CO, SO,SO₂; it can be further substituted by alkyl, OH, Oalkyl, Oaryl,Oaralkyl, COOH, COOalkyl, amidgroups or halogene;

Use

Compounds according to the invention are preferably used in the dyeproviding light-sensitive layers, in a quantity of 0.1 to 2 mol/mol ofcolor coupler, in particular in a quantity of 0.1 to 0.5 mol/mol ofcolor coupler.

Compounds according to the present invention are most preferably used inyellow dye providing blue-sensitive layers.

Compounds of the formula II, wherein D is a group—O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃ or a group —O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O—with W being a divalent amino group (—N(R₁₂)—, a polyamine residue, apolyethyleneimine residue or a polyoxyalkyleneamine residue can be usedalso for the controlled free radical polymerization of ethylenicallyunsaturated monomers.

Yellow couplers that can be used in combination with the dye stabilisersaccording to the invention are preferably compounds of the formula A:

wherein R₁ is alkyl, cycloalkyl, arylamino, anilino, a heterocyclicgroup or aryl, R₂ is aryl and Q is hydrogen or a group which can beeliminated by reaction with the oxidised developer.

One particularly preferred group of yellow couplers are those compoundsof formula A, wherein R₁ is t-butyl and R₂ is a group of formula

wherein R₃ is hydrogen, halogen, alkyl or alkoxy, and R₄, R₅ and R₆ arehydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxy,alkoxycarbonyl, a carbamoyl group, a sulfonic or sulfamoyl group, analkylsulfonamino group, acylamino group, ureido group or amino group. R₃is preferably chloro or methoxy, R₄ and R₅ are preferably hydrogen, andR₆ is preferably an acylamino group. This includes also the compounds offormula

wherein x is a number 0–4, R₇ is hydrogen or alkyl, and R₈ and R₉ arealkyl.

Another group of yellow couplers that can be used in combination withthe dye stabilisers according to the invention conforms to formula B:

wherein R₁₀ is hydrogen, halogen or alkoxy,

-   R₁₁, R₁₂ and R₁₃ are hydrogen, halogen, alkyl, alkenyl, alkoxy,    aryl, carboxyl, alkoxycarbonyl, a carbamoyl group, a sulfonic group,    sulfamoyl group, sulfonamido group, acylamino group, ureido group or    amino group, and R₁ and Q have the meaning cited above.

These couplers include compounds of formula B, in which R₁ is t-butyl,R₁₀ is chloro, R₁, and R₁₃ are hydrogen, and R₁₂ is alkoxycarbonyl.

In the compounds of formula A and B, the group Q may be hydrogen(4-equivalent coupler) or a heterocyclic group (2-equivalent coupler)

wherein R₁₄ is an organic divalent group which makes the ring up into a4–7-membered ring, or Q is a group —OR₁₅, wherein R₁₅ is alkyl, aryl,acyl or a heterocyclic radical.

Typical examples of customary yellow couplers are the compounds of thefollowing formulae (I to IV):

Particularly suited yellow couplers conform to formulae (Y-1) to (Y-19):

Further examples of suited yellow couplers are to be found in U.S. Pat.Nos. 2,407,210, 2,778,658, 2,875,057, 2,908,513, 2,908,573, 3,227,155,3,227,550, 3,253,924, 3,265,506, 3,277,155, 3,408,194, 3,341,331,3,369,895, 3,384,657, 3,415,652, 3,447,928, 3,551,155, 3,582,322,3,725,072, 3,891,445, 3,933,501, 4,115,121, 4,401,752 and 4,022,620,4,540,657, 5,001,045, 5,118,599, 5,183,731, 5,215,878, 5,260,182,5,294,527, 5,298,375, 5,298,383, 5,300,412, 5,306,609, 5,314,797,5,316,903, 5,336,591, 5,455,149, 5,441,855, 5,466,569, 5,521,058,

in DE-A 1,547,868, 2,057,941, 2,162,899, 2,163,813, 2,213,461,2,219,917, 2,261,361, 2,261,362, 2,263,875, 2,329,587, 2,414,006 and2,422,812; in GB-A 1,425,020 and 1,077,874, and in JP-A-88/123,047, U.S.Pat. Nos. 4,133,052, 5,080,469, 5,313,323; in JP-A 08-286338, -234381,-160578, -160577, -160576, and in EP-A-447,969, 447,920, 508,398,510,535, 542,463, 568,198, 710,882, 751,428 and EP-B-482,552.

The yellow couplers are customarily used in an amount of 0.05–2 mol,preferably of 0.1–1 mol, per mol of silver halide.

Examples of colour photographic materials according to this inventionare colour negative films, colour reversal films, colour positive films,colour photographic paper, colour reversal photographic paper,colour-sensitive materials for the dye diffusion transfer process or thesilver dye bleach process.

Typical bases for silver halide photographic materials include polymericfilms and polymer-coated paper. Details regarding supports for colourphotographic recording materials can be found in Research Disclosure,Item 36544, September 1994.

Examples of suitable bases for the production of colour photographicmaterials are films and sheets of semisynthetic and synthetic polymers,such as cellulose nitrate, cellulose acetate, cellulose butyrate,polystyrene, polyvinyl chloride, polyethylene terephthalate,polyalkylene naphthalate (e.g. as disclosed in U.S. Pat. No. 5,824,465)and polycarbonate, and paper laminated with a barytes layer or anα-olefin polymer layer (e.g. polyethylene). These bases can have beencoloured with dyes or pigments, for example titanium dioxide. They canalso have been coloured black for the purposes of light shielding. Thesurface of the base is generally subjected to a treatment for improvingthe adhesion of the photographic emulsion layer, for example coronadischarge with subsequent application of a substrate layer.

Essential constituents of the colour-photographic emulsion layers arebinders, silver halide particles and colour couplers. Details regardingthe constituents of light sensitive layers and other (non lightsensitive) layers such as top layers and interlayers separating thesilver halide emulsion layers can be found in Research Disclosure, Item38957, September 1996.

The binder used is preferably gelatin. However, gelatin may be replacedentirely or in part by other synthetic, semisynthetic or naturallyoccurring polymers. Synthetic gelatin substitutes are, for example,polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamide, polyacrylicacid or their derivatives, in particular their copolymers. Naturallyoccurring gelatin substitutes are, for example, other proteins such asalbumin or casein, cellulose, sugar, starch or alginates. Semisyntheticgelatin substitutes are as a rule modified natural products. Examplesthereof are cellulose derivatives, such as hydroxyalkylcellulose, andgelatin derivatives, which are obtained by reaction with alkylating oracylating agents or by being grafted with polymerisable monomers.

The binders should contain a sufficient amount of functional groups sothat it is possible to produce sufficiently resistant layer by reactionwith suitable hardeners. Such functional groups are, in particular,amino groups and also carboxyl groups, hydroxyl groups and activemethylene groups.

The halide in the silver halide present in the photographic material asphotosensitive component can contain chloride, bromide or iodide, ormixtures thereof. The halide in at least one layer can, for example,consist to 0 to 15 mol % of iodide, to 0 to 100 mol % of chloride and to0 to 100 mol % of bromide. In the case of colour negative and colourreversal films, it is usual to use silver bromide iodide emulsions, inthe case of colour negative and colour reversal papers silver chloridebromide emulsions having a high chloride content, for example at least90 mol % silver chloride up to pure silver chloride emulsions. They maybe predominantly compact crystals which are e.g. regularly cubic oroctaedric or which can have transition forms. Preferably, however, it isalso possible to use platy crystals having an average ratio of diameterto thickness of preferably at least 5:1, the diameter of a grain beingdefined as the diameter of a circle having a circular area correspondingto the projected area of the grain. The layers can, however, alsocontain platy silver halide crystals having a ratio of diameter tothickness which is substantially higher than 5:1, for example from 12:1to 30:1.

The silver halide grains may also have a multi-layered grain structure,in the simplest instance having an inner and outer grain area(core/shell), the halide composition and/or other modifications, e.g.dopings of the individual grain areas, being different. The averagegrain size of the emulsions is preferably in the range of 0.2 mm to 2.0mm, and the grain size distribution can be both homo- andheterodisperse. Homodisperse grain size distribution means that 95% ofthe grains do not deviate more than ±30% from the average grain size.Besides the silver halide, the emulsions can also contain organic silversalts, for example silver benzotriazolate or silver behenate.

Two or more kinds of silver halide emulsions, prepared separately, maybe used as a mixture.

The photographic emulsions can be prepared from soluble silver salts andsoluble halides by different methods (e.g. P. Glafkides, Chimie etPhysique Photographiques, CEP Editions, Paris (1987), G. F. Duffin,Photographic Emulsion Chemistry, The Focal Press, London (1966), V. L.Zelikman et al, Making and Coating Photographic Emulsion, The FocalPress, London (1966)).

The silver halide emulsions are usually subjected to a chemicalsensitization under defined conditions—pH, pAg, temperature, theconcentration of gelatin, silver halide and sensitiser—until optimumsensitivity and fogging is reached. The process is described, interalia, in H. Frieser “Die Grundlagen der Photographischen Prozesse mitSilverhalogeniden” p. 675–734, Akademische Verlagsgesellschaft (1968).

The chemical sensitization can be carried out with addition of sulfur,selenium, tellurium compounds and/or compounds of the metals of theVIIIth side group of the periodic system (e.g. gold, platinum,palladium, iridium). It is also possible to add thiocyanate compounds,surfactants, such as thioethers, heterocyclic nitrogen compounds (e.g.imidazoles, azaindenes) or also spectral sensitisers (described, interalia, in F. Hamer “The Cyanine Dyes and Related Compounds”, 1964, or inUllmanns Encyclopadie der technischen Chemie, 4^(th) edition, Vol. 18,p. 431 ff, and in Research Disclosure 17643 (December 1978), chapterIII). Instead or additionally, it is possible to carry out a reductionsensibilisation with addition of reduction agents (tin-II-salts, amines,hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid)by means of hydrogen, low pAg (e.g. lower than 5) and/or high pH (e.g.above 8).

The photographic emulsions might contain compounds for preventingfogging or for stabilising the photographic function during production,storage or photographic processing.

Azaindenes are particularly suitable, preferably tetra- andpentaazaindenes, more preferably those which are substituted by hydroxylgroups or amino groups. Such compounds have been described, for example,by Birr, Z. Wiss. Phot. 47 (1952), p. 2–58. Antifogging agents used maybe, for example, salts of metals, such as of mercury or cadmium,aromatic sulfonic or sulfinic acids, such as benzenesulfinic acid, ornitrogen-containing heterocycles, such as nitrobenzimidazole,nitroindazole, unsubstituted or substituted benzotriazoles orbenzothiazolium salts. Mercapto group-containing heterocycles areparticularly suitable, e.g. mercaptobenzothiazoles,mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles,mercaptopyrimidines, which mercaptoazoles can also contain awater-solubilising group, for example a carboxyl group or sulfo group.Other suitable compounds are published in Research Disclosure 17643(December 1978).

The stabilisers can be added to the silver halide emulsions before,during or after their ripening. It is also possible to add the compoundsalso to other photographic layers allocated to a silver halide layer.

It is also possible to use mixtures of two or more of the citedcompounds.

The photographic emulsion layers or other hydrophilic colloid layers ofthe photosensitive material prepared according to this invention cancontain surfactants for different purposes, such as coating aids, agentsfor preventing electrical charging, lubricants, agents for emulsifyingthe dispersion, agents for preventing adhesion and agents for improvingthe photographic characteristics (e.g. development accelerators, highcontrast, sensibilisation etc.). Besides natural surfactants, e.g.saponin, synthetic surfactants are mainly used; non-ionic surfactants,e.g. alkylene oxide compounds, glycerin compounds or glycidol-compounds,cationic surfactants, e.g. higher alkylamines, quarternary ammoniumsalts, pyridine compounds and other heterocyclic compounds, sulfoniumcompounds or phosphonium compounds, anionic surfactants containing anacid group, e.g. a carboxylic acid, sulfonic acid, phosphoric acid, asulfate or phosphate group, ampholytic surfactants, e.g. amino acid andaminosulfonic acid compounds, and also sulfates or phosphates of anamino alcohol.

The photographic emulsions are usually spectrally sensitised usingmethine dyes or other dyes. Particularly suitable dyes are cyanine dyes,merocyanine dyes and complex merocyanine dyes.

Research Disclosure 17643 (December 1978), provides an overview of thepolymethine dyes suitable as spectral sensitisers, of their suitablecombinations and of combinations which act as supersensitisers.

Particularly suitable dyes are the following dyes, listed according totheir spectral ranges:

1. As Red Sensitisers

-   9-ethylcarbocyanine containing benzothiazole, benzoselenazole or    naphthothiazole as basic end groups which may be substituted in 5-    and/or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, as    well as 9-ethylnaphthoxathia- or -selencarbocyanines and    9-ethylnaphthothiazoxa- or -benzimidazocarbocyanines, provided the    dyes carry at least one sulfoalkyl group at the heterocyclic    nitrogen.    2. As Green Sensitisers-   9-ethylcarbocyanines containing benzoxazole, naphthoxazole or a    benzoxazole and a benzothiazole as basic end groups and also    benzimidazocarbocyanines, which can likewise be further substituted    and which also contain at least one sulfoalkyl group at the    heterocyclic nitrogen.    3. As Blue Sensitisers-   symmetrical or asymmetrical benzimidazo-, oxa-, thia- or    selenacyanines containing at least one sulfoalkyl group at the    heterocyclic nitrogen and, optionally, additional substituents at    the aromatic nucleus, and apomerocyanines containing a rhodanine    group.

It is possible to forego the use of sensitisers if the inherentsensitivity of the silver halide, for example the blue sensitivity ofsilver bromides, is sufficient for a specific spectral range.

To the differently sensitised emulsion layers are allocatednon-diffusing monomeric or polymeric colour couplers, which may belocated in the same layer or in an adjacent layer. It is common toassign cyan couplers to the red-sensitive layers, magenta couplers tothe green-sensitive layers and yellow couplers to the blue-sensitivelayers.

Cyan couplers are typically of the phenol, naphtol or pyrazoloazoletype.

Magenta couplers are, for example, simple 1-aryl-5-pyrazolones, orpyrazole derivatives condensed with 5-membered hetero rings, such asimidazopyrazoles, pyrazolopyrazoles, pyrazolotriazoles orpyrazolotetrazoles.

Examples of magenta and cyan couplers that can be used in a photographicmaterial according to the present invention can be found in GB A 2 343007, which is included herein as reference, as well as in referencescited therein.

Yellow couplers are generally couplers with an open chain ketomethylenegroup, in particular couplers of the α-acylacetamide type. Suitableexamples of yellow couplers are given above.

Colour couplers might be 4-equivalent or 2-equivalent couplers. Thelatter are differentiated from 4-equivalent couplers by containing asubstituent at the coupling position, which is eliminated upon couplingwith colour developer oxidation products.

The couplers customarily contain a ballast residue in order to preventintra- and interlayer wandering. High molecular weight couplers might beused instead and are described, inter alia, in DE-A-1297417,DE-A-2407569, DE-A-3148125, DE-A-3217200, DE-A-3320079, DE-A-3324932,DE-A-3331743, DE-A-3340376, EP-A-27284, U.S. Pat. No. 4,080,211. Thehigh molecular weight colour couplers are usually prepared bypolymerisation of ethylenically unsaturated monomeric colour couplers.However, they can also be obtained by polyaddition or polycondensation.

The incorporation of the couplers or other compounds, including thestabilizers according to this invention, in a silver halide emulsionlayer can be carried out such that a solution, dispersion or emulsion isprepared from the respective compound, which is then added to thecasting solution used for the layer in question. Selection of theappropriate solvent or dispersant depends on the particular solubilityof the compound.

Methods for the incorporation of compounds which are essentiallyimmiscible in water by grinding processes are described, inter alia, inDE-A-2609741, DE-A-2609742 and in EP-A-694590. The grinding process canbe complemented by a thermal process by heating the emulsion to abovethe melting point of the compounds to be dispersed, with rapidsubsequent cooling (EP-B-515674). Dispersants for the stabilisation ofdispersions of solid particles are described, inter alia, in U.S. Pat.No. 5,591,568.

Hydrophobic compounds can also be incorporated in the casting solutionsusing high-boiling solvents, so-called oil formers. Correspondingmethods are described, inter alia, in U.S. Pat. Nos. 2,322,027,2,801,170, 2,801,171 and EP-A-0043037.

The high-boiling solvents can be replaced with oligomers or polymers,so-called polymeric oil formers.

The compounds can also be incorporated in the casting solution in theform of loaded latices, see for example DE-A-2541230, DE-A-2541274,DE-A-2835856, DE-A-19536376, EP-A-0014921, EP-A-0069671, EP-A-0130115,U.S. Pat. No. 4,291,113.

The diffusion-stable incorporation of anionic water-soluble compounds(e.g. of dyes) can also be carried out by means of cationic polymers,so-called mordant polymers.

The compounds according to this invention can be incorporated singly ortogether with the colour coupler and, optionally, other additives in thecolour photographic material by predissolving them in high-boilingorganic solvents.

Suitable high-boiling solvents are, for example, alkyl phthalates,phosphonates, phosphorates, citrates, benzoates, amides, fatty acidesters, trimesinates, alcohols, phenols, aniline-derivatives andhydrocarbons.

Examples of suitable high-boiling solvents are dibutylphthalate,dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate,triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate,tridecylphosphate, tributoxyethylphosphate, trichloropropylphosphate,di-2-ethylhexylphenylphosphate, 2-ethylhexylbenzoate, dodecylbenzoate,2-ethylhexyl-p-hydroxybenzoate, diethyldodecanamide,N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t—amylphenol,dioctylacelate, glycerol tributyrate, isostearyllactate,trioctylcitrate, N,N-dibutyl-2-butoxy-5-t-octylaniline, paraffin,didecylbenzene and diisopropylnaphthalene.

The amount of high-boiling solvent used is in the range of, for example,50 mg to 2 g per m² support, preferably of 200 mg to 1 g per m².

A low-boiling solvent might be used in addition to the oil former, inorder to simplify incorporation of hydrophobic compounds into thecolour-photographic recording material.

Examples of such solvents are esters, for example ethyl acetate,alcohols, for example butanol, ketones, for example methyl isobutylketone, chlorinated hydrocarbons, such as methylene chloride, andamides, such as dimethylformamide. Where the compounds themselves areliquid, they can also be incorporated into the photographic materialwithout the assistance of oil formers.

The photographic layers in the material of this invention mayalso-include UV absorbers, which screen out the UV light and thereforeprotect the dyes, the couplers or other components againstphotodegradation.

Preferred UV absorbers to be used in a photographic material accordingto the present invention include benzotriazoles,2-hydroxybenzophenrones, oxanilides, cyanoacrylates, salicylic esters,acrylonitrile derivatives, thiazolines and 2-hydroxyphenyltriazines.

Such UV absorbers are described in more detail, for example, in thefollowing publications: U.S. Pat. Nos. 3,314,794, 3,352,681, 3,705,805,3,707,375, 4,045,229, 3,700,455, 3,700,458, 3,533,794, 3,698,907,3,705,805, 3,738,837, 3,762,272, 4,163,671, 4,195,999, 4,309,500,4,431,726, 4,443,543, 4,576,908, 4,749,643,5500332, 5455152,GB-A-1,564,089, GB-A-2,293,608, EP-A-190,003, -747755, -717313 andJP-A-71/2784, 81/111,826, 81/27,146, 88/53,543, 88/55,542 and 96/69087;and U.S. Pat. Nos. 5,300,414, 5,489,503, 5,480,108, 4,826,978,EP-A-706083, JP-A-08-267915, U.S. Pat. No. 5,364,749, WO 96/28431,GB-A-2319523. Particularly preferred UV absorbers are listed inGB-A-2343007.

The amount of the UV absorber or absorbers added is judiciously in therange from 0.001 to 10 g per m², for example from 0.1 to 8 g/m²,especially from 0.005 to 6 and, in particular, from 0.01 to 4 g/m².

The photographic material can furthermore contain fluorescent whiteningagents, spacers, filter dyes, formalin scavengers, light stabilisers,antioxidants, D_(min) dyes, additives for improving the stability ofdyes, couplers and whites and for reducing color stain, plasticisers(latices), biocides and other materials.

The non-photosensitive interlayers, which are usually arranged betweenlight sensitive layers of different spectral sensitivity, usuallycontain so-called oxidised developer scavengers, i.e. compounds thatprevent wandering of oxidised developer molecules from one silver halideemulsion layer to another one of different spectral sensitivity.Examples of suited oxidised developer scavengers can be found inResearch Disclosure 17643 (December 1978), 17842 (February 1979) and18716 (November 1979), and in EP-A-0069070, 0098072, 0124877, 0125522,871066 and GB-A-2343007; these include hydrazine, hydrazide,hydroquinone, 6-hydroxychroman, hydroxylamine and lactone derivatives.Particularly suited oxidised developer scavengers for use in aphotographic material according to this invention consist of thefollowing compounds:

Filter dyes suitable for visible light include oxonol dyes, hemioxonoldyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Ofthese, oxonol dyes, hemioxonol dyes and merocyanine dyes areparticularly advantageous to use.

Suitable fluorescent whitening agents are described, inter alia, inResearch Disclosure 17 643 (December 1978), chapter V, in U.S. Pat. Nos.2,632,701, 3,269,840 and in GB-A-852075 and 1319763.

Certain binder layers, in particular the layer farthest away from thesupport, but in some cases also an interlayer, especially if it is thelayer farthest away from the support during preparation, can containphotographically inert particles of inorganic or organic nature, forexample as matting agents or as spacers (DE-A-3331542; DE-A-3424893,Research Disclosure 17 643 (December 1978), chapter XVI).

The average particle diameter of the spacers is preferably in the rangeof 0.2 to 10 mm. The spacers are water-insoluble and may bealkali-insoluble or alkali-soluble, those which are soluble in alkaliusually being removed from the photographic material in the alkalinedeveloper bath. Examples of suitable polymers are polymethylacrylate,copolymers of acrylic acid and methylmethacrylate as well ashydroxypropylmethylcellulose-hexahydrophthalate.

Suitable formalin scavengers are for example:

The photographic material according to this invention might also containsubstances of formula

wherein Ya is —O—, —S— or —N(V₇)—;

-   V₁, V₇ are each independently of the other hydrogen, alkyl, aryl,    acyl or a heterocycle, for example methyl, i-propyl, benzyl,    hexadecyl, cyclohexyl, 2-phenoxyethyl, 2-methanesulfonamidoethyl,    tetrahydropyranyl, morpholinyl. All cited radicals (except H and    halogen) may be further substituted.

V₂–V₆ are each independently of one another hydrogen, Ya′—R₁′, halogen,alkyl, aryl, acyl, acylamino, alkoxycarbonyl, aryloxycarbonyl, sulfonyl,carbamoyl, sulfamoyl; Ya′ has the same meaning as Ya, and R₁′ has thesame meaning as R. All radicals (except H and halogen) may be furthersubstituted. R₂–R₆ are, for example, methyl, fluoro, chloro, bromo,t-octyl, benzyl, cyclohexyl, n-dodecyl, s-butyl,1,1-dimethyl-4-methoxycarbonylbutyl, acetyl, pivyloyl, dodecanoyl,benzoyl, 3-hexadecycloxybenzoyl, acetamino, pivaloylamino,2-ethylhexyanoylamino, 2-(2,4-di-t-amylphenoxy)octanoylamino,dodecanoylamino, methoxycarbonyl, dodecyloxycarbonyl,2,4-di-t-amylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, methanesulfonyl,4-dodecyloxybenzenesulfonyl, methylcarbamoyl, diethylcarbamoyl,N-methyl-N-phenylcarbamoyl.

Preferably, at least one of the V₂–V₆ substituents is Ya′—R₁′.

In addition, all the groups in ortho-position to one another in formulaA′ may make up a 5–8-membered ring (for example coumaran, chroman,indane, quinoline). These rings can further combine to form a bicyclicring or a spiroring.

V₁ and V₇ can make up a 5–7-membered, preferably a saturated ring (e.g.piperazine, morpholine or the like). The rings obtained can be furthersubstituted.

Such compounds are described, inter alia, in the following publications:U.S. Pat. No. 5,534,390; DE 19503885A1, U.S. Pat. Nos. 5,484,696;5,491,054, 5,200,307.

The compounds represented by the above formula A′ serve as lightstabilisers for the colour image and as agents against colour casts.They can be present in a photosensitive layer (colour layer) or in aninterlayer, singly or together with other additives. Such compounds aredescribed in more detail, inter alia, in the following publications:U.S. Pat. Nos. 3,700,455, 3,591,381, 3,573,052, 4,030,931, 4,174,220,4,178,184,4,228,235, 4,268,593, 4,279,990, 4,346,165, 4,366,226,4,447,523, 4,528,264, 4,581,326, 4,562,146, 4,559,297, 5,534,390;GB-A-1,309,277,1,547,302, 2,023,862, 2,135,788, 2,139,370, 2,156,091;DE-A-2,301,060, 2,347,708, 2,526,468, 2,621,203, 3,323,448, 19517072;DD-A-200,691, 214,468;EP-A-106,799,113,124,125,522,159,912,161,577,164,030,167,762,176,845,246, 766, 320, 776, 740204, 740205, 740206; JP-A-74/134,326, 76/127,730,76/30462, 77/3822, 77/154,632, 78/10842, 79/48535,79/70830, 79/73032,79/147,038, 79/154,325, 79/155,836, 82/142,638, 83/224,353, 84/5246,84/72443, 84/87456, 84/192,246, 84/192,247, 84/204,039, 84/204,040,84/212,837, 84/220,733, 84/222,836, 84/228,249, 86/2540, 86/8843,86/18835, 86/18836, 87/11456, 87/42245, 87/62157, 86/6652, 89/137,258and in Research Disclosure 79/17804.

Hydroquinone compounds, which are useful as light stabilisers for thecouplers and dyes and as oxidised developer scavengers, might also becontained in the photographic material according to this invention. Suchcompounds are predominantly used in magenta providing layers where thecoupler is of the pyrazolone type and in interlayers. Such hydroquinonecompounds and their combinations with other additives are described inmore detail, inter alia, in the following publications:

-   U.S. Pat. Nos. 2,360,290, 2,336,327, 2,403,721, 2,418,613,    2,675,314, 2,701,197, 2,710,801, 2,732,300, 2,728,659, 2,735,765,    2,704,713, 2,937,086, 2,816,028, 3,582,333, 3,637,393, 3,700,453,    3,960,570, 3,935,016, 3,930,866, 4,065,435, 3,982,944, 4,232,114,    4,121,939, 4,175,968, 4,179,293, 3,591,381, 3,573,052, 4,279,990,    4,429,031, 4,346,165, 4,360,589, 4,346,167, 4,385,111, 4,416,978,    4,430,425, 4,277,558, 4,489,155, 4,504,572, 4,559,297, 5,491,054,    5,484,696; FR-A-885,982; GB-A-891,158, 1,156,167, 1,363,921,    2,022,274, 2,066,975, 2,071,348, 2,081,463, 2,117,526, 2,156,091;    DE-A-2,408,168, 2,726,283, 2,639,930, 2,901,520, 3,308,766,    3,320,483, 3,323,699; DD-A-216,476, 214, 468, 214,469, EP-A-84290,    110,214, 115,305, 124, 915, 124,877, 144,288, 147, 747, 178,165,    161,577; JP-A-75/33733, 75/21249, 77/128,130, 77/146,234, 79/70036,    79/133,131, 81/83742, 81/87040, 81/109,345, 83/134,628, 82/22237,    82/112,749, 83/17431, 83/21249, 84/75249, 84/149,348, 84/182,785,    84/180,557, 84/189,342, 84/228,249, 84/101,650, 79/24019, 79/25823,    86/48856, 86/48857, 86/27539, 86/6652, 86/72040, 87/11455, 87/62157,    and in Research Disclosure 79/17901, 79/17905, 79/18813, 83/22827    and 84/24014.

Derivatives of hydroquinone ethers, which are particularly suitable forstabilising magenta dyes, might also be present. Such compounds andtheir combination with other additives are described in more detail e.g.in the following publications:

-   U.S. Pat. Nos. 3,285,937, 3,432,300, 3,519,429, 3,476,772,    3,591,381, 3,573,052, 3,574,627, 3,573,050, 3,698,909, 3,764,337,    3,930,866, 4,113,488, 4,015,990, 4,113,495, 4,120,723, 4,155,765,    4,159,910, 4,178,184, 4,138,259, 4,174,220, 4,148,656, 4,207,111,    4,254,216, 4,134,011, 4,273,864, 4,264,720, 4,279,990, 4,332,886,    4,436,165, 4,360,589, 4,416,978, 4,385,111, 4,459,015, 4,559,297;    GB-A 1,347,556, 1,366,441, 1,547,392, 1,557,237, 2,135,788; DE-A    3,214,567; DD-214,469, EP-A 161,577, 167,762, 164,130, 176,845; JP-A    76/123,642, 77/35633, 77/147,433, 78/126, 78/10430, 78/53321,    79/24019, 79/25823, 79/48537, 79/44521, 79/56833, 79/70036,    79/70830, 79/73032, 79/95233, 79/145,530, 80/21004, 80/50244,    80/52057, 80/70840, 80/139,383, 81/30125, 81/151,936, 82/34552,    82/68833, 82/204,306 82/204,037, 83/134,634, 83/207,039, 84/60434,    84/101,650, 84/87450, 84/149,348, 84/182,785, 86/72040, 87/11455,    87/62157, 87/63149, 86/2151, 86/6652, 86/48855, 89/309,058 and in    Research Disclosure 78/17051.

The photographic layers can also contain certain phosphorus-IIIcompounds, in particular phosphites and phosponites. These function aslight stabilisers for the colour formers and as dark storage stabilisersfor magenta couplers. They are preferably added to the high-boilingsolvents, together with the coupler. Such phosphorus-III compounds aredescribed in more detail e.g. in the following publications: U.S. Pat.Nos. 4,407,935, 4,436,811, 4,956,406, EP-A-181,289, JP-A-73/32728,JP-A-76/1420 and JP-A-55/66741.

The photographic layers can also contain organo-metallic complexes whichare light stabilisers for the colour formers, in particular for themagenta dyes. Such compounds and their combination with other additivesare described in more detail e.g. in the following publications: U.S.Pat. Nos. 4,050,938, 4,239,843, 4,241,154, 4,242,429, 4,241,155,4,242,430, 4,273,854, 4,246,329, 4,271,253, 4,242,431, 4,248,949,4,245,195, 4,268,605, 4,246,330, 4,269,926, 4,245,018, 4,301,223,4,343,886, 4,346,165, 4,590,153; JP-A-81/167,138, 81/168,652, 82/30834,82/161,744; EP-A-137,271, 161,577, 185,506, 740,204; DE-A-2,853,865.

The photographic material according ot this invention might also containconventional hindered amine light stabilisers, e.g.bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonicacid-bis(1,2,2,6,6-pentamethylpiperidyl)ester, the condensate of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine andalso 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No.[136504–96–6]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6—pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,the reaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin, malonicacid[(4-methoxyphenyl)—methylenebis(1,2,2,6,6-pentamethyl-4-piperidyl)]-diester,N,N′-bis-formyl-N,N′-bis(2,2,6,6—tetramethyl-4-piperidyl)hexamethylenediamine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic anhydride-α-olefin copolymer and2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

Further substances which might be used as light or dark stabilisers inthe photographic material according to this invention are described inU.S. Pat. Nos. 5,580,710, 5,543,276, 3,700,455, 4,782,011, 5,316,903,5,183,731, 5,070,007, 4,268,593 and DE 10006978.

Especially suited dye stabilisers are those of formulae (ST-1) to(ST-38). The stabilisers according to the present invention might beused in combination with them.

The layers of the photographic material can be cured using customaryhardeners. Suitable hardeners are, for example, formaldehyde,glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadioneand similar ketone compounds, bis(2-chloroethylurea),2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds containingreactive halogen (U.S. Pat. Nos. 3,288,775, 2,732,303, GB-A-974723 andGB-A-1167207), divinylsulfone compounds,5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other compoundscontaining a reactive olefin bond (U.S. Pat. No. 3,635,718, U.S. Pat.No. 3,232,763 and GB-A-994869); N-hydroxymethylphthalimide and otherN-methylol compounds (U.S. Pat. Nos. 2,732,316 and 2,586,168);isocyanates (U.S. Pat. No. 3,103,437); aziridine compounds (U.S. Pat.Nos. 3,017,280 and 2,983,611); acid derivatives (U.S. Pat. Nos.2,725,294 and 2,725,295); carbodiimide type compounds (U.S. Pat. No.3,100,704); carbamoylpyridinium salts (DE-A-2225230 and U.S. Pat. No.2,439,511); carbamoylpyridinium compounds (DE-A-2408814); compoundscontaining a phosphorus-halogen bond (JP-A-113929/83); N-carbonyloximidecompounds (JP-A-43353/81); N-sulfonyloximido compounds (U.S. Pat. No.4,111,926), dihydroquinoline compounds (U.S. Pat. No. 4,013,468),2-sulfonyloxypyridinium salts (JP-A-110762/81), formamidinium salts(EP-A-0162308), compounds containing two or more N-acyloximino groups(U.S. Pat. No. 4,052,373), epoxy., compounds (U.S. Pat. No. 3,091,537),isoxazole type compounds (U.S. Pat. Nos. 3,321,313 and 3,543,292);halocarboxyaldehydes, such as mucochloric acid; dioxane derivatives,such as dihydroxydioxan and dichlorodioxan; and inorganic hardeners,such as chrome alum and zirconium sulfate.

Curing can be effected in known manner by adding the hardener to thecasting solution used for the layer to be cured, or by coating the layerto be cured with a layer containing a hardener capable of diffusion.

The classes listed here include both hardeners which act slowly andthose which act rapidly, such as so-called instant hardeners which areparticularly advantageous. Instant hardeners are understood to becompounds which crosslink suitable binders such that, immediately aftercasting, at the latest after 24 hours, preferably at the latest after 8hours, curing is completed to such a degree that there is no change ofthe sensitometry and of the swelling of the layer compound caused by thecrosslinking reaction. Swelling is understood to mean the differencebetween wet layer thickness and dry layer thickness when the film isprocessed in water (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci.,Eng. (1972), 449).

These hardeners which react very rapidly with gelatin are, for example,carbamoylpyridinium salts capable of reacting with free carboxyl groupsof the gelatin so that the latter react with free amino groups of thegelatin with formation of peptide bonds and crosslinking of the gelatin.

There are hardeners capable of diffusion which act as hardeners for alllayers within one multi-layer film. However, there are also low and highmolecular weight hardeners, the action of which is restricted to onelayer and which do not diffuse. Using these it is possible to crosslinkindividual layers, e.g. the protective layer, particularly strongly.This is important when the silver halide layer hardens little due to thesilver hiding power and the mechanical properties must be improved withthe protective layer (EP-A-0114699).

Colour photographic negative materials are usually processed bydeveloping, bleaching, fixing and washing, or by developing, bleachingfixing and stabilising without subsequent washing, it being possible tocombine bleaching and fixing to one processing step. The colourdevelopment compound used may be all developer compounds having theability of reacting in the form of their oxidation product with colourcouplers to azomethine or indophenol dyes. Suitable colour developercompounds are aromatic p-phenylenediamine type compounds containing atleast one primary amino group, for exampleN,N-dialkyl-p-phenylenediamines such as N,N-diethyl-p-phenylenediamine,1-(N-ethyl-N-methanesulfonamidoethyl)-3-methyl-p-phenylenediamine and1-(N-ethyl-N-methoxyethyl)-3-methyl-p-phenylenediamine. Other suitablecolour developers are described, for example, in J. Amer. Chem. Soc. 73,3106 (1951) and G. Haist, Modern Photographic Processing, 1979, JohnWiley and Sons, New York 545 ff.

Colour development may be followed by an acid stopping bath or washing.

The material is usually bleached and fixed immediately after colourdevelopment. Bleaches used may be, for example, Fe(III) salts andFe(III) complex salts, such as ferricyanides, dichromates, water-solublecobalt complexes. It is particularly preferred to use iron-(III)complexes of aminopolycarboxylic acids, in particular e.g. those ofethylenediaminetetraacetic acid, propylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiaceticacid, N-hydroxyethylethylenediamintriacetic-acid, alkyliminodicarboxylicacids and of corresponding phosphonic acids. Other suitable bleaches arepersulfates and peroxides, e.g. hydrogen-peroxide.

The bleaching-fixing bath or fixing bath is usually followed by washingwhich is carried out as countercurrent washing or using several tankswith individual water inlets.

Favourable results can be obtained using a subsequent final bath whichcontains no, or only little, formaldehyde.

Washing can, however, be completely replaced by a stabilising bath whichis usually carried out in countercurrent. If formaldehyde is added, thisstabilising bath also functions as a final bath.

In the case of colour reversal materials, development is first carriedout using a black-and-white developer, the oxidation product of which isnot capable of reacting with the colour couplers. A subsequent diffusesecondary exposure is followed by development with a colour developerand then by bleaching and fixing.

Besides their use in colour photographic materials, compounds of formula(Ia), (Ib) or (IIc) can also find utility in other recording materials,such as digital recording materials, for example, those forpressure-sensitive copying systems, microcapsule photocopier systems,heat-sensitive copier systems and ink-jet printing.

The novel recording materials feature an unexpectedly high quality,especially in terms of their light stability.

The novel recording materials have a structure which is known per se andwhich corresponds to the utility. They consist of a base, for examplepaper or plastic film, on which one or more coatings are applied.Depending on the type of material, these coats contain the suitablecomponents required, in the case of photographic material for examplesilver halide emulsions, colour couplers, dyes and the like. Thematerial intended especially for ink-jet printing has a customary baseon which there is an absorption layer suitable for ink. Uncoated papercan likewise be employed for ink-jet printing; in this case, the paperfunctions simultaneously as a base and has the absorbent for the ink.Suitable material for ink-jet printing is described, inter alia, in U.S.Pat. No. 5,073,448, the disclosure content of which is regarded as partof the present description.

The recording material can also be transparent, for example in the caseof projection films.

The compound(s) of the invention can be incorporated into the materialeven in the course of manufacture; in papermaking, for example, byaddition to the pulp. Another method of use is the spraying of thematerial with an aqueous solution of compound(s) of the invention, orthe addition thereof to the coating.

Coatings for transparent recording materials for projection must notcontain any light-scattering particles such as pigments or fillers.

The colour-binding coatings can contain further additives, for exampleantioxidants, light stabilisers (including UV absorbers), viscosityimprovers, brighteners, biocides and/or antistats.

The coating is usually prepared as follows:

The water-soluble components, for example the binder, are dissolved inwater and mixed.

The solid components, for example fillers and other additives as alreadydescribed, are dispersed in this aqueous medium. Dispersion isadvantageously brought about with the aid of equipment such asultrasonic devices, turbine agitators, homogenisers, colloid mills, beadmills, sand mills, high-speed stirrers and the like. A particularadvantage of the compounds of the invention is their ease ofincorporation into the coating.

As mentioned, the novel recording materials cover a broad field of use.Compounds of the invention can be employed, for example, inpressure-sensitive copier systems. They can be added to the paper toprotect the microencapsulated dye precursors against light, or to thebinder of the developer layer to protect the dyes formed therein.

Photocopier systems with light-sensitive microcapsules which aredeveloped by pressure are described, inter alia, in U.S. Pat. Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,5365,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A-139,479; EP-A-162,664;EP-A-164,931; EP-A-237,024; EP-A-237,025 and EP-A-260,129. In all thesesystems the compounds of the invention can be added to thecolour-accepting layer. Alternatively, the compounds of the inventioncan be added to the donor layer for protecting the colour formersagainst light.

The compounds of the invention can also be employed in recordingmaterials which are based on the principle of photopolymerisation,photosoftening or the rupture of microcapsules, or when heat-sensitiveor photosensitive diazonium salts, leuco dyes with oxidising agent orcolour lactones with Lewis acids are used.

Heat-sensitive recording material exploits the colour-imparting reactionbetween a colourless or weakly coloured base dye and an organic orinorganic colour developer, the recorded image being produced byheat-induced contact of the two materials. This type of heat-sensitiverecording material is very widespread, not only as the recording mediumfor faxes, computers, etc., but also in many other fields, for examplein label printing.

The heat-sensitive recording material according to the present inventionis composed of a base, a heat-sensitive colour-forming recording layeron this base, and, optionally, a protective layer on the heat-sensitive,colour-forming recording layer. The heat-sensitive, colour-formingrecording layer contains as its principal constituent a colour-impartingcompound and a colour-developing compound, and also a compound of theinvention. If the said protective layer is present, the compounds of theinvention can also be incorporated into the protective layer.

Heat-sensitive recording materials are described, for example, in JP-A8–267 915.

Further fields of use are recording materials for dye diffusion transferprinting, thermal wax transfer printing and dot matrix printing, and foruse with electrostatic, electrographic, electrophoretic, magnetographicand laser-electrophotographic printers, recorders or plotters. Of thematerials mentioned, preference is given to recording materials for dyediffusion transfer printing, as are described, for example, inEP-A-507,734.

The novel recording material preferably contains 1 to 10,000 mg/m², inparticular 50–2,000 mg/m², of at least one compound of the formulae(Ia), (Ib) or (IIc).

Compounds of the invention can also be employed in inks, preferably forink-jet printing, for example those as described in U.S. Pat. No.5,098,477, the disclosure content of which is regarded as part of thepresent description. The invention therefore also provides an inkcomprising at least one compound of the invention as stabiliser. Theinks according to the invention contain at least one dye. In this regardthe nature of the ink and the dye dissolved in it and the type ofprinter used are immaterial. The ink, especially for ink-jet printing,contains preferably water.

In many printers a distinction is drawn between those which have acontinuous ink jet and “drop-on-demand” printers, in particularbubble-jet printers. The ink according to the invention can be used forthe equipment of all these processes, specifically for printing ink jetprinting paper and films.

The inks are in most cases aqueous inks, but they can also be solutionsof the dye in an organic solvent or in a melted wax. In most casesaqueous inks still contain water-soluble solvents, for example mono-,di- or tri-ethylene glycols or higher ethylene glycols, propyleneglycol, 1,4-butanediol or ethers of such glycols, thiodiglycol, glyceroland ethers and esters thereof, polyglycerol, mono-, di- andtri-ethanolamine, propanolamine, dimethylformamide, dimethyl sulfoxide,dimethylacetamide, N-methylpyrrolidone, 1,3-dimethylimidazolidone,methanol, ethanol, isopropanol, n-propanol, diacetone alcohol, acetone,methyl ethyl ketone or propylene carbonate.

Aqueous inks contain water-soluble dyes such as are also known fordyeing natural fibers. These can, for example, be monoazo, disazo orpolyazo dyes, reactive dyes, triphenylmethane dyes, xanthene dyes orphthalocyanine dyes. Examples of these are Food Black 2, C.I. DirectBlack 19, C.I. Sulphur Black 1, Acid Red 35, Acid Red 52, Acid Yellow 23and copper phthalocyanines, and also Direct Black 38, Direct Black 168,Acid Red 249, Direct Red 227, Direct Yellow 86, Acid Blue 9, Direct Blue86 and Direct Blue 199. Aqueous inks can also contain various additivesin minor amounts, for example binders, surfactants, biocides, corrosioninhibitors, sequestering agents, pH buffers or conductivity additives.They can also contain water-soluble UV absorbers or other water-solublelight stabilizers. In general, however, the addition, according to theinvention, of a stabilizer of the formula I to the ink is adequate.

If the ink is a non aqueous ink, it is a solution of the dye in anorganic solvent or solvent mixture. Examples of solvents used for thispurpose are alkyl carbitols, alkylcellosolves, dialkylformamides,dialkylacetamides, alcohols, especially alcohols having 1–4 C atoms,acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone,diisopropyl ketone, dibutyl ketone, dioxane, ethyl butyrate, ethylisovalerate, diethyl malonate, diethyl succinate, methyl pelargonate,butyl acetate, triethyl phosphate, ethylglycol acetate, toluene, xylene,tetralin or petroleum fractions. Examples of solid waxes as solvents,which, as an ink, must first be heated, are stearic or palmitic acid.

Inks of this type based on solvents contain dyes soluble therein, forexample Solvent Red, Solvent Yellow, Solvent Orange, Solvent Blue,Solvent Green, Solvent Violet, Solvent Brown or Solvent Black. Inks ofthis type too can also contain further additives, such as are mentionedabove for aqueous inks.

Inks contain the stabiliser of the invention usually in a concentrationof from 0.01 to 20% by weight, in particular from 0.5 to 10% by weight.

EXAMPLES Example 1 (Preparation according WO99/46261) Preparation of2,2,6,6-tetramethyl-1-(1-(4-oxiranylmethoxy-phenyl)-ethoxy)-4-propoxypiperidine

Compound II with A=—CH₂—CHY—CH₂—; Y=OR₁₄, R₃=—C(R₁₀)₂—X—D, R₁₀=H, CH₃,X=phenylene, D=

A: A 70% aqueous solution of tert.-butylhydroperoxyde (26.4 g) isextractively dehydrated in two portions with each of 25 g2-(4-ethyl-phenoxymethyl)-oxirane. The organic extracts are combined, amolecular sieve is added and the mixture is stored under argonatmosphere.

B: A mixture of 2-(ethyl-phenoxymethyl)-oxirane (57 g),4-propoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (10.7 g) andmolybdenum(VI)oxide (0.72 g) are purged with Argon for one hour. Themixture is then heated up to 70° C. and the solution prepared under A)is added under stirring within 30 minutes. Pressure is reduced to 200mbar and the mixture is heated for 18 hours at 100° C. After thereaction is completed the mixture is cooled to room temp. and thepressure is allowed to raise to normal pressure. Ethylacetate and wateris added. The water phase is separated and extracted once withethylacetate. The organic phases are combined, washed with a 10%solution of sodium ascorbate and in a second step with water, dried oversodium sulfate and concentrated. Excessive amounts of2-(4-ethyl-phenoxymethyl)-oxirane are removed at 80° C./0.01 mbar. Theraw product is subsequently chromatographically purified on silica withpetrolether/ethylacetate 7/1 as eluent. A clear colorless oil isobtained, corresponding to the compound of formula (101)

Elemental Analysis: calculated C₂₃H₃₇NO₄: 70.55%, C; 9.52%, H; 3.57%, N.found: 70.66%, C; 9.60%, H; 3.43%, N.

Example 2 (Preparation According to WO02/48109) Preparation of7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-Phenyl)-ethoxy]-1.4-dioxa-8-aza-spiro[4.5]decan

Compound II with A=—CH₂—C(OZ)(OZ′)—CH₂—; Z and Z′ form a bivalent group—CH₂—CH₂—, R₃=—C(R₁₀)₂—X—D, R₁₀=H, CH₃, X=phenylene, D=

A mixture of 50 g7,7,9,9-tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl (preparedaccording to EP 574666A1) and 124.75 g 2-(4-ethyl-phenoxymethyl)-oxiranare heated to 600° C. with stirring and a solution of 0.32 gcopper(II)chloride in 1.6 ml ethanol is added. 45 g of an aqueoussolution of butylhydroperoxide in water (70%) is dropwise added. Thereaction mixture is allowed to further react for 16 h at 60° C. andsubsequently cooled to room temperature. Excess tert.-butylhydroperoxideis removed by dropwise adding 15 ml of an aqueous sodium pyrosulfitesolution. To the reaction mixture 100 ml acetic acid ethylester areadded and the organic and aqueous phase are separated. The organic phaseis washed twice with 200 ml of a saturated NaCl solution. After dryingwith sodium sulfate and evaporation of the solvent an oil is obtained,from which excess 2-(4-ethyl-phenoxymethyl)-oxiran is removed bydistillation (100° C./0.005 mbar). The residue is dissolved in hexanefiltered over aluminium oxide and the solvent is again evaporated. Afterrecrystalization from hexane white crystals are obtained having amelting point of 73.5–74.2° C.

Example 3 Preparation of3,3,8,8,10,10-hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecan

Compound II with A=—CH₂—C(OZ)(OZ′)—CH₂—; Z and z form a bivalent group—CH₂—C(CH₃)(CH₃)CH₂—, R₃=—C(R₁₀)₂—X-D, R₁₀=H, CH₃, X=phenylene, D=

The title compound is prepared in analogy to Example 2 from3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl(prepared according to EP 574666A1). White crystals are obtained.

Elemental analysis: calculated: 69.25%, C; 9.07%, H; 3.23%, N; found:68.86%, C; 9.05%, H; 3.18%, N.

Preparation of the New Compounds Example 4 Preparation of1-Dimethylamino-3-[4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenoxy]-propan-2-ol

Compound II with A=—CH₂—C(OZ)(OZ)—CH₂—; Z and Z′ form a bivalent group—CH₂—C(CH₃)(CH₃)CH₂—, R₃=—C(R₁₀)₂—X—D, R₁₀=H, CH₃, X=phenylene,D=—O—CH₂—CH(OH)—CH₂—N(CH₃)₂

A solution of 4.33 g3,3,8,8,10,10-Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecaneprepared according to PCT/EP/01/13071 and 1.46 g diethylamine inmethanol (15 ml) was stirred at reflux for 2 h. After evaporation ofmethanol a highly viscous resin was obtained. Stirring the resin inwater (100 ml) for two days gave a white suspension. The suspension wasfiltered and washed with water. After vacuum drying a colourless powderwas obtained having a melting point of 77–83° C.

Example 5 Preparation of1-[4-[1-(3,3,8,8,10,10-Hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenoxy}-3-pyrrolidin-1-yl-propan-2-ol

Compound II with A=—CH₂—C(OZ)(OZ′)—CH₂—; Z and Z′ form a bivalent group—CH₂—C(CH₃)(CH₃)CH₂—, R₃=—C(R₁₀)₂—X—D, R₁₀=H, CH₃, X=phenylene,D=—O—CH₂—CH(OH)—CH₂—N(R₁₂)(R₁₃); R₁₂ and R₁₃ form a ring

The compound of Example 5 is prepared according to Example 4 usingpyrrolidine.

Example 6 Preparation of1-Diethylamino-3-[4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenox}-propan-2-ol

Compound II with A=—CH₂—C(OZ)(OZ′)—CH₂—; Z and Z′ form a bivalent group—CH₂—C(CH₃)(CH₃)CH₂—, R₃=—C(R₁₀)₂—X—D, R₁₀=H, CH₃, X=phenylene,D=—O—CH₂—CH(OH)—CH₂—N(C₂H₅)₂

The compound of Example 6 is prepared according to Example 4 usingdiethylamine.

Example 7 Preparation of1-{4-[1-(3,3,8,8,10,10-Hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenoxy}-3-[4-(3-{4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undec-9-yloxy)-ethyl]-phenoxy}-2-hydroxy-propyl)-piperazin-1-yl]-propan-2-ol

Compound II with A=—CH₂—C(OZ)(OZ′)—CH₂—; Z and Z′ form a bivalent group—CH₂—C(CH₃)(CH₃)CH₂—, R₃=—C(R₁₀)₂—X—D′, R₁₀=H, CH₃, X=phenyleneD′=—O—CH₂—CH(OH)—CH₂-piperazine-CH₂—CH(OH)—CH₂—O—,

To a solution of 8,67 g3,3,8,8,10,10-Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecanein tetrahydrofurane (24 ml) was added 0,86 g piperazine. The reactionmixture was stirred at reflux over night then evaporated to dryness. Theresinous residue is stirred in methanol (25 ml) until a homogenoussuspension was formed. The suspension was filtered, the residue washedwith icecold methanol (15 ml) and dryed at room temperature. A whitepowder was obtained melting at 137–142° C.

Example 8Butyl-(2-hydroxy-3-{4-[1-(2,2,6,6-tetramethyl-4-propoxy-piperidin-1-yloxy)-ethyl]-phenoxy}-propyl)-amino]-3-{4-[1-(2,2,6,6-tetramethyl-4-propoxy-piperidin-1-yloxy)-ethyl]-phenoxy}-propan-2-ol

Compound II with A=—CH₂—CH(Y)—CH₂—; Y is alkoxy;

-   R₃=—C(R₁₀)₂—X-D′, R₁₀=H, CH₃, X=phenylene,-   D′=—O—CH₂—CH(OH)—CH₂—N(alkyl)-CH₂—CH(OH)—CH₂—O—,

Example 8 is prepared according to Example 7 using butylamine.

Example 9

Compound II with A=—CH₂—CH(Y)—CH₂—; Y is alkoxy,

-   R₃=—C(R₁₀)₂—X—D′, R₁₀=H, CH₃, X=phenylene,-   D′=—(O—CH₂—CH(OH)—CH₂—)₂—N—CH₂—CH₂—N—(CH₂—CH(OH)—CH₂—O)₂—,

Example 9 is prepared according to Example 7 using ethylendiamine.

APPLICATION EXAMPLES Example A1

Photographic test elements are prepared by providing layers of followingcomposition on a polyethylene-coated paper support:

Component Amount in mg · m⁻² Gelatine 5150 AgBr 520 (based on silver)Yellow coupler Y1  973 Stabilizer according to  292 inventionDibutylphthalate  324 Hardener H1  300 Surfactant S1  340 Antifoggant A1  4

After drying, the produced samples are exposed to white light behind astep wedge with density increment 0.30 and thereafter processed in thecustomary manner according to the P94 process (Agfa-Gevaert).

The samples are then evaluated for light fastness by exposing themthrough an ultraviolet filter in an Atlas weatherometer equipped with aXenon lamp. The light fastness is evaluated based on the percentage ofdensity loss after 60 kJ.cm⁻² exposure.

In a second experiment, yellow step images obtained in the abovedescribed way are stored in the dark at 80° C., 70% relative humidity.The dark stability is evaluated based on the percentage of density lossafter 4 weeks storage.

TABLE I Density Density loss (%) upon loss (%) upon Xenon exposure darkstorage at density at density Sample Stabilizer 1.0 D_(max) 1.0 D_(max)I-1 (control) — 60 78 36 37 I-2 (comparison) ST-12 29 38 32 34 I-3(comparison) ST-33 32 25 36 28 I-4 (comparison) ST-39 39 59 36 36 I-5(invention) ST-A 19 7 31 32 I-6 (invention) ST-B 16 3 20 30 I-7(invention) ST-C 17 8 27 29 I-8 (invention) ST-D 21 11 29 32 I-9(invention) ST-E 16 7 28 28

As table I shows, the compounds according to the invention provide theyellow image with much improved light stability, especially at highdensity. In addition, improved dark stability of the yellow dye isachieved.

Example A2

Photographic test elements are prepared by providing layers of followingcomposition on a polyethylene-coated paper support:

Component Amount in mg · m⁻² Gelatine 5150 AgBr 520 (based on silver)Yellow coupler Y2  859 Stabilizer according to  258 inventionDibutylphthalate  286 Hardener H1  300 Surfactant S1  340 Antifoggant A1  4

After drying, the produced samples are exposed to white light behind astep wedge with density increment 0.30 and thereafter processed in thecustomary manner according to the P94 process (Agfa-Gevaert).

The samples are then evaluated for light fastness by exposing themthrough an ultraviolet filter in an Atlas weatherometer equipped with aXenon lamp. The light fastness is evaluated based on the percentage ofdensity loss after 90 kJ.cm ² exposure.

TABLE II Density loss (%) upon Xenon exposure at density SampleStabilizer 1.0 D_(max) II-1 (control) — 27 42 II-2 (comparison) ST-33 2112 II-3 (comparison) ST-39 22 20 II-4 (comparison) ST-26 23 29 II-5(invention) ST-A 21 9 II-6 (invention) ST-B 15 4 II-7 (invention) ST-C22 12 II-8 (invention) ST-D 20 9 II-9 (invention) ST-E 21 6

The above table shows that the compounds according to the inventionimprove substantially the light stability of the yellow photographicimage, especially at high density.

Coupler Y1

Coupler Y2

Hardener H1 Surfactant S1 Antifoggant A1

Stabilizer ST-A Stabilizer ST-B

Stabilizer ST-C

Stabilizer ST-D Stabilizer ST-E

1. A colour photographic material which contains on a support at leastone blue-sensitive silver halide emulsion layer containing at least oneyellow coupler, at least one green-sensitive silver halide emulsionlayer containing at least one magenta coupler, at least onered-sensitive silver halide emulsion layer containing at least one cyancoupler, together with non-light-sensitive layers, wherein at least onelayer contains a compound of the formula (I) or (II)

wherein the R₁-radicals are each independently of one another hydrogen,halogen, NO₂, cyano, —CONR₅R₆, —(R₉)COOR₄, —C(O)—R₇, —OR₈, —SR₈, —NHR₈,—N(R₈)₂, carbamoyl, di(C₁–C₁₈alkyl)carbamoyl, —C(═NR₅)(NHR₆);unsubstituted C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈alkynyl,C₇–C₉phenylalkyl, C₃–C₁₂cycloalkyl or C₂–C₁₂heterocycloalkyl; orC₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈ alkynyl, C₇–C₉phenylalkyl,C₃–C₁₂cycloalkyl or C₂–C₁₂heterocycloalkyl, which are substituted byNO₂, halogen, amino, hydroxy, cyano, carboxy, C₁–C₄alkoxy,C₁–C₄alkylthio, C₁–C₄alkylamino or di(C₁–C₄alkyl)-amino; or phenyl,naphthyl, which are unsubstituted or substituted by C₁–C₄alkyl,C₁–C₄alkoxy, C₁–C₄alkylthio, halogen, cyano, hydroxy, carboxy,C₁–C₄alkylamino or di(C₁–C₄alkyl)amino; R₄ is hydrogen, C₁–C₁₈alkyl,phenyl, an alkali metal cation or a tetraalkylammonium cation; R₅ and R₆are hydrogen, C₁–C₁₈alkyl, C₂–C₁₈alkyl, which is substituted by at leastone hydroxy group or, taken together, form a C₂–C₁₂alkylene bridge or aC₂–C₁₂-alkylene bridge interrupted by at least one O or NR₈ atom; R₇ ishydrogen, C₁–C₁₈alkyl or phenyl; R₈ is hydrogen, C₁–C₁₈alkyl orC₂–C₁₈alkyl which is substituted by at least one hydroxy group; R₉ isC₁–C₁₂alkylene or a direct bond; or all the R₁-radicals form togetherthe residue of a polycyclic cycloaliphatic ring system or a polycyclicheterocycloaliphatic ring system with at least one di- or trivalentnitrogen atom; the R₂-radicals are independently of each otherC₁–C₆alkyl or phenyl; R₃ is a radical of the formula —C(R₁₀)R₁₀)—X—D,wherein X is phenylene, naphthylene or biphenylene, which areunsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano,carboxy, C₁–C₄alkoxy, C₁–C₄alkylthio, C₁–C₄alkylamino ordi(C₁–C₄alkyl)amino; the R₁₀-radicals are independently of each other Hor CH₃; D is a group

or a group —C(O)—C₁–C₁₈alkyl or a group —C(O)—R₁₁—C(O)—C₁–C₁₈alkyl; withR₁₁ being a bond or C₁–C₁₂alkylene, or a group—O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, wherein R₁₂ and R₁₃ independently of oneanother are unsubstituted C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈alkynyl,phenyl, C₇–C₉phenylalkyl, C₃–C₁₂cycloalkyl; the radicals may beinterrupted once or more than once by —, —NH—, —O—, —S—, —CO—, —SO—,—SO₂—, or C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈ alkynyl, phenyl,C₇–C₉phenylalkyl, C₃–C₁₂cycloalkyl, which are substituted by halogen,amino, hydroxy, carboxy, C₁–C₆alkoxy, C₁–C₆alkoxycarbonyl,C₁–C₆alkylthio, C₁–C₆alkylamino or di(C₁–C₆alkyl)-amino,C₁–C₆alkylamino-carbonyl or di(C₁–C₆alkyl)-amino-carbonyl; the radicalsmay be interrupted once or more than once by —, —NH—, —O—, —S—, —CO—,—SO—, —SO₂—, or R₁₂ and R₁₃ together with N form a 4 to 8 membered ring,whereby the ring may be interrupted by —O—, —NH—, S—, —CO—, —SO—, —SO₂and may be sustituted by carboxy, or D is a group—O—CH₂—CH(OH)—CH₂—N(R₁₂)—CH₂—CHOH—CH₂—O— or—O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O— with W being a divalent amino group(—N(R₁₂)—), a polyamine residue, a polyethyleneimine residue or apolyoxyalkyleneamine residue; A is a divalent group required to form acyclic 5-, 6- or 7-membered ring, whereby the divalent group is selectedfrom C₂–C₄alkylene, C₂–C₄alkenylene, C₂–C₄alkinylene, 1,2 phenylenewhich may be unsubstituted or substituted by NO₂, halogen, amino,hydroxy, cyano, carboxy, carbonyl, C₁–C₁₈alkoxy, C₁–C₁₈ acyloxy,benzoyloxy, C₁–C₁₈alkylthio, C₁–C₁₈alkylamino or di(C₁–C₁₈alkyl)amino,or phenyl; or A is a group —CH₂—CHY—CH₂—, wherein Y is H, OH, OR₁₄,NR₁₅R₁₆, —O—C(O)—R₁₇ or NR₁₅—C(O)—R₁₇; R₁₄ is C₁–C₁₈alkyl,C₂–C₁₈alkenyl, C₂–C₁₈alkinyl, phenyl, benzyl, mesityl, or C₂–C₁₈alkylwhich is substituted by at least one hydroxy group; R₁₅ and R₁₆independently are hydrogen, C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈alkinyl,or taken together form a C₂–C₁₂alkylene bridge or a C₂–C₁₂alkylenebridge interrupted by at least one O atom; R₁₇ is phenyl, benzyl,mesityl, C₁–C₁₈alkyl, C₂–C₁₈alkenyl, C₂–C₁₈alkinyl; or A is a group—CH₂—C(OZ)(OZ′)—CH₂—, wherein Z and Z′ are independently C₁–C₁₂alkyl,C₃–C₁₂alkenyl, C₃–C₁₂alkinyl, C₅–C₈cycloalkyl, phenyl, naphthyl,C₇–C₉phenylalkyl; or Z and Z′ together form one of the bivalent groups—C(R₁₈)(R₁₉)—CH(R₂₀)—, —CH(R₁₈)—CH₂—C(R₁₉)(R₂₀)—,—CH(R₁₉)—CH₂—C(R₁₈)(R₂₀)—, —CH₂—C(R₁₈)(R₁₉)—CH(R₂₀)-o-phenylene,1,2-cyclohexylidene, —CH₂—CH═CH—CH₂— or

wherein R₁₈ is hydrogen, C₁–C₁₈alkyl, COOH, COO—(C₁–C₁₈)alkyl,OCO—(C₁–C₁₈)alkyl or CH₂OR₂₁; R₁₉ and R₂₀ are independently hydrogen,C₁–C₁₂alkyl, COOH or COO—(C₁–C₁₂)alkyl; R₂₁ is hydrogen, C₁–C₁₈alkyl,C₅–C₆cycloalkyl, benzyl, or a monovalent acyl residue derived from analiphatic, cycloaliphatic or aromatic monocarboxylic acid having up to18 carbon atoms; or Z and Z′ together form one of the tetravalent groups

wherein Q is a bisacyl residue which is derived from aC₂–C₁₂dicarboxylic acid or C₁–C₁₂alkylene.
 2. A colour photographicmaterial according to claim 1, containing a compound of the formula I,wherein R₁ is methyl and R₃ is a radical —CH(CH₃)—X—D, wherein X isphenylene, D is a group

or a group —C(O)—C₁–C₁₈alkyl or a group —O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, withR₁₂ and R₁₃ being C₁–C₁₈alkyl or together form a 4 to 8 membered ring asdefined in claim 1, or D is a group—O—CH₂—CH(OH)—CH₂—N(R₁₂)—CH₂—CHOH—CH₂—O— or—O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O— with W being a divalent amino group(—N(C₁–C₁₈alkyl)—), a polyamine residue, a polyethyleneimine residue ora polyoxyalkyleneamine residue.
 3. A colour photographic materialaccording to claim 1, containing a compound of the formula II, whereinR₂ is methyl and A is a group —CH₂—CHY—CH₂—, thus having a structure ofthe formula IIa

wherein R₃ and Y are as defined in claim
 1. 4. A colour photographicmaterial according to claim 3, wherein Y is H, OH, OR₁₄, —O—C(O)—R₁₇,R₁₄ is C₁–C₁₈alkyl, phenyl, benzyl, mesityl, R₁₇ is C₁–C₁₈alkyl, phenyl,benzyl, mesityl, R₃ is a radical —CH(CH₃)—X—D wherein X is phenylene, Dis a group

or a group —C(O)—C₁–C₁₈alkyl or a group —O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, withR₁₂ and R₁₃ being C₁–C₁₈alkyl or together form a 4 to 8 membered ring asdefined in claim 1, or D is a group—O—CH₂—CH(OH)—CH₂—N(R₁₂)—CH₂—CHOH—CH₂—O— or—O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O— with W being a divalent amino group(—N(C₁–C1₈alkyl)—), a polyamine residue, a polyethyleneimine residue ora polyoxyalkyleneamine residue.
 5. A colour photographic materialaccording to claim 1, containing a compound of the formula II, wherein Ais a group —CH₂—C(OZ)(OZ′)—CH₂—, thus having a structure of the formulaIIb

wherein R₃, Z and Z′ are as defined in claim
 1. 6. A colour photographicmaterial according to claim 5, wherein R₃ is a radical —CH(CH₃)—X—Dwherein X is phenylene, D is a group

or a group —C(O)—C₁–C₁₈alkyl or a group —O—CH₂—CH(OH)—CH₂—NR₁₂R₁₃, withR₁₂ and R₁₃ being C₁–C₁₈alkyl or together form a 4 to 8 membered ring asdefined in claim 1, or D is a group—O—CH₂—CH(OH)—CH₂—N(R₁₂)—CH₂—CHOH—CH₂—O— or—O—CH₂—CH(OH)—CH₂—W—CH₂—CHOH—CH₂—O— with W being a divalent amino group(—N(C₁–C1₈alkyl)—), a polyamine residue, a polyethyleneimine residue ora polyoxyalkyleneamine residue.
 7. A method of providing resistance tolight or dark fade of photographic dyes by incorporating compounds ofthe formula I or II as defined in claim 1 in the dye providinglight-sensitive layers, in a quantity of 0.1 to 2 mol/mol of colorcoupler.
 8. A method according to claim 7 of providing resistance tolight or dark fade of photographic dyes by incorporating compounds ofthe formula I or II as defined in claim 1 in the dye providinglight-sensitive layers in a quantity of 0.1 to 0.5 mol/mol of colorcoupler.
 9. A method according to claim 7 of providing resistance tolight or dark fade of photographic dyes by incorporating compounds ofthe formula I or II as defined in claim 1 in the yellow dye providingblue light-sensitive layer.
 10. A dye providing light-sensitivephotographic layer comprising at least one of the compounds of theformula I or II according to claim 1 in a quantity of 0.1 to 2 mol/molof color coupler.
 11. A dye providing light-sensitive photographic layercomprising at least one of the compounds of the formula I or IIaccording to claim 1 in a quantity of 0.1 to 0.5 mol/mol of colorcoupler.
 12. A yellow dye providing blue light-sensitive photographiclayer comprising at least one of the compounds of the formula I or IIaccording to claim 1 in a quantity of 0.1 to 2 mol/mol of color coupler.